Sizing compositions



Patented Dec. 5, 1950 SIZING COMPOSITIONS Fred Fortess, Summit, N. J.,and Marshall Duke,

Cumberland, Md., assignors to Celanese Corporation of America, acorporation of Delaware No Drawing.

Application December 8, 1948,

Serial No. 64,234

8 Claims.

This invention relates to sizing compositions and relates moreparticularly to compositions particularly adapted to be employed for thesizing of spun yarns comprising staple fibers having a basis ofcellulose acetate or other organic derivative of cellulose.

An object of this invention is the provision of an improved compositionfor the sizing of spun yarns of staple fibers having a basis ofcellulose acetate or other organic derivative of cellulose.

Another object of this invention is the provision of a composition forthe sizing of fine count spun yarns of staple fibers having a basis ofcellulose acetate or other organic 'derivative of cellulose to enablesaid fine count yarns to be woven as a warp in the production of fabricmaterials.

A further object of this invention is to provide a novel composition forthe sizing of fine count spun yarns having a basis of cellulose acetateor other organic derivative of cellulose staple fibers which not onlyacts as a sizing composition but which also simultaneously lubricatesand conditions the spun yarns for weaving operations.

Other objects of this invention will appear from the following detaileddescription.

As is well known i the art, warps of spun yarns are normally sized priorto being employed in weaving operations. The object of applying sizingcompositions to the yarns is to form a film or coating thereon whichstrengthens the yarns and renders them more resistant to abrasion duringweaving operations which tends to weaken or sever the yarns and toproduce end breaks. In spite of the application of sizes of varyingcomposition to spun yarns comprising staple fibers of cellulose acetateor other organic derivative of'cellulose, an excessive number of endbreaks is encountered in the weaving of fine count warp yarns and,particlularly, yarns of 20/1 or finer. Since the end breaks have to beknotted together to continue weaving, the quality of the fabric isreduced and, inthe past, has been so serious as to render the weaving ofspun yarns of cellulose acetate or other organic derivative of cellulosestaple fiber of a count of 20/ 1 or finer commercially impractical. i

We have now found that if warps of spun yarns of 20/ 1 count and finerare sized with an improved composition having both a sizing andlubricating action on said spun yarns, the warps obtained may be woveninto commercially acceptable fabric in an efficient and economicalmanner with a substantially reduced number of end breaks.

The novel sizing composition of our invention comprises an aqueoussolution of polyvinyl alcohol containing a humidifying agent such asglycerine, sorbitol, pentaerythritol, polyethylene glycol and urea, andhaving a lubricant composition and a conditioning composition dispersedtherein. The film-forming polyvinyl alcohol in our novel sizingcomposition acts to bind the staple fibers comprising the spun yarnwhile the lubricant and conditioning compositions incorporated in thesize reduce frictional and static ef fects which tend to impair fabricquality.

The lubricant composition which we employ comprises a plurality ofcomponents including mineral oil, an oxidized vegetable oil, a dialkylphenol, an alkylolamine and a higher fatty acid. The lubricantcomposition may also contain an acyl derivative of an ester of ahydroxylated higher fatty acid in which the acylradical is derived froma lower fatty acid. The conditioning composition comprises thede'salted, dehydrated product, diluted with mineral'oiLobtained onreacting oleum with a mixture of mineral oil, a vegetable oil and ahigher fatty ac'idto which has been added a penetrating agent such as adialkyl phenol and which has been neutralized with an alkali such assodium hydroxide prior to salt removal and dehydration.

The lubricant composition is preferably prepared, for example, by mixingmineral oil with a suitable quantity of oxidized peanut oil, or oxidizedsperm oil, oxidized olive oil or oxidized teaseed oil, adding a dialkylphenol, preferably branch chained, such as, di-secondary ordi-tertiary-butyl phenol or di-secondary or. di-tertiaryamyl phenol, analkylolamine such as triethanolamine, and a higher fatty-acid such asoleic acid. Butyl acetyl ricinoleate or other acyl derivative of anester of a hydroxylated higher fatty acid may also be added. Usually,themineral oil comprises 50 to about by weight ofthe mixture, theoxidized vegetable oil is about 20% by weight, the

- dialkyl phenol about 10% by weight and the acylated higher fatty acidester about 10% by weight. The long chain fatty acid and alkylolamineconstitute the remainder and are usually added in stoichiometricproportions so as to form an alkylolamine soap of the fattyacid; A .verysmall amount of a blending agent such as oleyl alcohol may also beemployed. The preparation of the lubricant compositions described andwhich constitutes one of the components of our novel yarn size is moreparticularly described in U. S. Patent No. 2,385,423, all of thecompositions dis- Q QS Q therein being suitable for use as the lubriacidor palmitic with fuming sulfuric acid such.

as oleum, at a temperature no greater than about 20 C. Under theseconditions at least part of the aliphatic acid and the vegetable oilemployed are sulfated and/or sulfonated. At the completion of thesulfation and/or sulfonation reaction, an alkylated phenol, such asdibutyl or diamyl phenol is added to the reaction mixture to stabilizethe same and to act as a pene-.

trant and an anti-oxidant. The addition of the alkyl phenol is followedby the addition of a sufficient amount of an alkali metal hydroxide toneutralize all of the sulfuric acid remaining and the major portion ofthe free aliphatic acid. The

batch is then stirred until reaction ceases and a clear oil is formed.

The sulfated and/or sulfonated reaction product obtained in the mannerdescribed above is subjected to a de-salting and dehydration treatmentbefore it is diluted with mineral oil and employed as a component of mynovel sizing composition. The de-salting and dehydration is effected bydiluting the neutralized reaction product with an organic solvent suchas anhydrous isopropyl alcohol which is a non-solvent for the inorganicsalts present and which forms an azeotrope with water. The alcoholaddition causes the salts to be precipitated from solution. Theprecipitated salts are then filtered out and the isopropyl alcoholdistilled off, the water which is present in the mixture coming off asan azeotrope with the isopropyl alcohol. Preferably, the temperature ofthe sulfonated mixture being distilled should not exceed about 110 C.during the distillation operation. If any water remains, an additionalquantity of anhydrous isopropyl alcohol is then added and the dilutedmixture again distilled to remove the remaining water as well as thealcohol. Prior to distillation, a filter aid such as diatomaceous earthor bentonite, for example, may be added and the solution filtered toimprove the clarity and remove any inorganic salts still present. Thestill residue remaining after distillation comprises the compositionemployed as the salt-free, dehydrated component. The latter is dilutedwith added mineral oil prior to use in forming our novel size. To obtainthe desired degree of dilution about 40 parts by weight of thesalt-free, dehydrated product are added to about 60 parts by weight ofmineral oil.

To form the novel sizing composition of our invention from about to 85parts by weight of polyvinyl alcohol are mixed with about 10 to 40 partsby weight of glycerine, 6.5 to 19.5 parts by weight of themulticomponent lubricant composition and 3.5 to 10.5 parts by weight ofthe mineral oil-diluted desalted, dehydrated sulfated and/or sulfonatedreaction product and the whole then diluted with 400 to 1200, and,preferably about 800 parts by weight of water. After thorough mixing,the size composition is in suitable dilution for application to a warpof spun yarns having a basis of cellulose acetate or other organicderivative of cellulose staple fibers. The size may be applied to thewarp in the usual manner employing a slasher or the like.

The components of our novel size composition are not entirely compatibleand the composition is preferably agitated during application of thesize to a warp. Our novel composition contains a balance of oilcomponents which are not compatible with the polyvinyl alcohol filmwhich is formed and, on drying, the oil components in the sizecomposition are, in part, forced to the surface. Thus, the polyvinylalcohol film acts to bind the yarn fibers while the oil componentsimpart the desired lubricity.

In order further to illustrate our invention, but without being limitedthereto, the following examples are given:

I Example I A mixture suitable for use as the lubricant compositioncomponent in forming the novel size of my invention is formed bythoroughly mixing the following components in the proportions given:

Parts by weight Parafiin base white mineral oil (50 seconds viscosity)55.05 Oxidized peanut oil 20.2 Oleic acid 10.35 Di-tertiary-amyl phenol4.55 Triethanolamine 4.80

Butyl acetyl ricinoleate 5.05

Example II The de-salted, dehydrated component of our novel sizingcomposition is prepared as follows:

A mixture of 117 parts by weight of acid-refined white mineral oil ofabout 50 Saybolt viscosity at F., 89 parts by weight of oleic acid, and43 parts by weight of raw peanut oil are cooled to 8 to 10 C. in asuitable vessel provided with a cooling jacket and then 27 parts byweight of 20% oleum are added over a period of one-half hour. Thetemperature rises due to the exothermic nature of the reaction but themaximum temperature is held to below 25 C. by cooling. The reactionmixture is then stirred for an additional 45 minutes with thetemperature held at 20 C. To the reaction mixture, there are now added21 parts by weight of diamyl phenol, followed by the added to 75 partsby weight of a 25% by weight aqueous solution of sodium hydroxide. Theresulting neutralized mixture is cooled to room temperature withstirring.

The sulfonated reaction mixture obtained is then desalted by theaddition thereto of anhydrous isopropyl alcohol to precipitate theinorganic salts present and the latter are then removed by filtration.The flltered solution is distilled under vacuum and the isopropylalcohol and water are taken oil as an azeotropic mixture with the stilltemperature held at a maximum of.

C. The still residue is diluted with an equal volume of anhydrousisopropyl alcohol, about 0.1 to 0.4% by weight of a diatomaceous earthfilter aid are added and the mixture filtered again. The isopropylalcohol present and any remaining water are removed by repeating thedistillation under vacuum at a maximum still temperature of 110 C. Thestill residue comprises the desalted and dehydrated reaction productwhich, after dilution with mineral oil in a ratio of-40 parts by weightof the still residue to 60 parts by weight of mineral oil, isincorporated in said diluted form as a component 01 our novel sizinxcomposition.

Example III In order to prepare our novel sizing composition, thefollowing are mixed together:

Parts by weight After mixingthoroughly to disperse the components in thewater the size is ready for use in a slasher. During use, the size ispreferably continuously agitated as it is applied to the warp.

A 43 inch warp of 2752 ends of /1 spun yarn of a blend consisting of 45%2 denier per filament, by weight of 3 denier per filament and 25% byweight of 5.5 denier per filament cellulose acetate staple fiber, all ofan average fiber length of 2 inches, is sized with the above sizecomposition. The sized warp is then woven into a. tabby weave fabricwith a filling of 54 picks per inch of the above blended 20/1 spun yarn.In a total length of 183 yards only 34 end breaks were found to haveoccurred for an average of only 0.19 end breaks per running yard.Normally, without the use of our novel size, end breaks of over 1.0 perrunning yard are encountered when trying to weave the 20/ 1 spun yarn asa warp.

While the application of the novel size of our invention has beendescribed more particularly in connection with the sizing of fine countspun cellulose acetate yarns, equally valuable results may be obtainedwhere the spun yarns have av basis of other organic derivative ofcellulose materials. Examples of other organic derivative of cellulosematerials are cellulose esters such as cellulose propionate,cellulosebutyrate, cellulose acetate-propionate and'celluloseacetate-butyrate as well as cellulose esters such as ethyl cellulose andbenzyl cellulose. Furthermore, while the use of our novel size for thesizing of warps of fine count spun yarns has, been stressed, it is to beunderstood that'ou'r novel size may also be employed for the sizingofcoarser counts of organic derivative of cellulose staple fiber spunyarns, spun yarns of fibers of other textile materials or evencontinuous filament yarns.

It is to be understood that the foregoing detailed description is givenmerely by wa of illustration and that many variations may be madetherein without departing from the spirit of our invention.

Having described our invention, what we desire to secure by LettersPatent is:

1. A composition for the sizing of textile yarns. comprising a mixturein water of polyvinyl alcohol, a humidifying agent; a lubricantcomposition comprising a mixture of mineral oil, an oxidized vegetableoil, a dialkyl phenol, an alkylolamine and a higher fatty acid; and aconditioning agent comprising the desalted and. dehydratedalkalineutralized reaction product of oleum with a mixture of a higherfatty acid, a vegetable oil and mineral oil, which reaction product hasbeen diand dehydrated alkali-neutralized reaction product of oleum witha mixture of a higher fatty acid, a vegetable oil and mineral oil havingpenetrating agent incorporated therein,v which reaction product has beendiluted with mineral oil.

3. A composition for the sizing of textile yarns, comprising a mixturein water of polyvinyl alcohol, a humidifying agent; a lubricantcomposition comprising a mixture of mineral oil, an oxidized vegetableoil, a dialkyl phenol, an alkylolamine, a higher fatty acid, anacylderivative of an ester of a hydroxylated higher fatty acid in whichthe acyl radical is derived from a lower fatty acid, and a blendingagent; and a conditioning composition comprising the desalted anddehydrated alkali-neutralized reaction product of oleum with a mixtureof a higher fatty acid, a vegetable oil and mineral oil having apenetrating agent incorporated therein, which reaction product has beendiluted with mineral oil.

4. A composition for the sizing of textile yarns, comprising a mixturein water of polyvinyl alcohol, glycerine; a lubricant compositioncomprising a, mixture of mineral oil, an oxidized vegetable oil, adialkyl phenol, an alkylolamine, a higher fatty acid, an acyl derivativeof an ester of a hydroxylated higher fatty acid in which the acylradical is derived from a lower fatty acid and a blending agent; and aconditioning composition comprising the desalted and dehydratedalkali-neutralized reaction product of oleum with a mixture of a higherfatty acid, a vegetable oil and mineral oil having a penetrating agentincorporated therein, which reaction product has been diluted withmineral oil.

5. A composition for the sizing of textile yarns, comprising a mixturein about 800 parts by weight of water of about 25 to parts by weight ofpolyvinyl alcohol, about 10 to 40 parts by weight of glycerine; about6.5 to 19.5 parts by weight of a lubricant composition comprising amixture of mineral oil, an oxidized vegetable oil, a dialkyl phenol, analkylolamine, a higher fatty acid, an acyl derivative of an ester of ahydroxylated higher fatty acid in which the acyl radical is derived fromlower fatty acid and a blending agent; about 3.5 to 10.5 parts by weightof a conditioning composition comprising the desalted and dehydratedalkali-neutralized reaction product of oleum with a mixture of a higherfatty acid, a vegetable oil and mineral oil having a penetrating agentincorporated therein, which reaction product has been diluted withmineral oil.

6. A composition for the sizing of textile yarns, comprising a mixturein water of polyvinyl alcohol, glycerine; a lubricant compositioncomprising a mixture of mineral oil, oxidized peanut oil, diamyl phenol,triethanolamine, oleic acid, butyl acetyl ricinoleate and oleyl alcohol;a conditioning composition comprising the desalted, dehydrated sodiumhydroxide neutralized reaction product with oleum of a mixture of oleicacid. peanut oil and mineral oil having a diamyl phenol incorporatedtherein, which reaction product has been diluted with mineral oil. I

7. A composition for the sizing of textile yarns, comprising a mixturein about 400 to 1200 parts by weight of water, of about 25 to' 85 partsby parts by weight of a conditioning composition comprising thedesalted, dehydrated sodium hydroxide neutralized reaction product witholeum of a mixture of oleic acid, peanut oil and mineral oil. and havinga diamyl phenol incorporated therein, which reaction product has beendilute with mineral oil.

8. A composition for the sizing of textile yarns.

comprising a mixture in about 400 to 1200 parts by weight of water, ofabout 25 to 85 parts by weight of polyvinyl alcohol, about 10 to 40parts by weight of glycerlne; about 6.5 to 19.5 parts by weight 01' alubricant composition comprising a mixture of mineral oil, oxidizedpeanut oil, diamyl phenol, triethanolamine, oleic acid,-;butyl acetylricinoleate and oleyi alcohol; about 3.5 to 10.5 4 parts-by weight of aconditioning composition comprising the desalted, dehydrated sodiumhydroxide neutralized reaction product with oleum of a mixture of oleicacid, peanut oil and mineral oil, and having a diamyl phenolincorporated therein, which reaction product has been diluted with about60% by weight oi mineral oil on the weight 01 the composition.

FRED FORTESS.

MARSHALL DUKE.

REFERENCES 'The following references are of record in the file oi. thispatent:

UNITED STATES PATENTS 1 Number Name Date 2,324,601 Spanagel July 20,1943 2,385,423 Seymour et a1 Sept. 25, 1945 2,406,408 Seymour et a1.Aug. 27. 1946

1. A COMPOSITION FOR THE SIZING OF TEXTILE YARNS, COMPRISING A MXTURE INWATER OF POLYVINYL ALCOHOL, A HUMIDIFYING AGENT; A LUBRICANT COMPOSITIONCOMPRISING A MIXTURE OF MINERAL OIL, AN OXIDIZED VEGETABLE OIL, ADIALKYL PHENOL, AND ALKYLOLAMINE AND A HIGHER FATTY ACID; AND ACONDITIONING AGENT COMPRISING THE DESALTED AND DEJYDRATEDALKALINEUTRALIZED REACTION PRODUCT OF OLEUM WITH A MIXTURE OF A HIGHERFATTY ACID, A VEGETABLE OIL AND MINERAL OIL, WHICH REACTION PRODUCT HASBEEN DILUTED WITH MINERAL OIL.